KR20170044193A - 2-(2,3-epoxypropyl)phenol composition and method of making - Google Patents

Abstract

The present invention discloses a process for preparing 2- (2,3-epoxypropyl) phenol by reacting 2-allylphenol with an oxidizing agent in the presence of a catalyst. 3-chromanol can be formed as a by-product. This method can be used to prepare 2- (2,3-epoxypropyl) -6-methylphenol. Transition metal catalysts and peroxide oxidizing agents may be used. The present invention also relates to a process for the preparation of a pharmaceutical composition comprising 1 to 90% by weight of 2- (2,3-epoxypropyl) phenol, 5 to 90% by weight of 2-allylphenol and 0 to 40% Composition, especially 1 to 90% by weight 2- (2,3-epoxypropyl) -6-methylphenol, 5 to 90% by weight 2-allyl-6-methylphenol and 8- 0% to 40% by weight of the composition.

Description

2- (2, 3-epoxypropyl) phenol composition and a process for producing the same.

The present invention relates to 2- (2,3-epoxypropyl) phenol compositions and processes for their preparation.

2- (2,3-epoxypropyl) phenol is a C-glycidylphenol in which a 2,3-epoxypropyl group or glycidyl group is directly bonded to the phenyl ring carbon atom, and glycidyl group is bonded to the phenol oxygen atom Is different from O-glycidylphenol or glycidylphenyl ether bonded thereto. 2- (2,3-Epoxypropyl) phenol is potentially a useful reagent for thermosetting resins, especially epoxy resins, thanks to its epoxy functionality. A process for the production of 2- (2,3-epoxypropyl) phenols which is efficient and inexpensive to make into commercial materials is desirable. In order to lower the cost, this method should have the following features. This method should be based on inexpensive materials available in large quantities and should be a one-step reaction and have a commercially acceptable cycle time (time between batches, when making batches).

The present invention provides a process for preparing 2- (2,3-epoxypropyl) phenol, comprising reacting 2-allylphenol with an oxidizing agent in the presence of a catalyst,

The 2-allylphenol

, Wherein the 2- (2,3-epoxypropyl) phenol is selected from the group consisting of

/ RTI >

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C ₁ -C ₁₂ hydrocarbyl-oxy, or C ₂ -C for at least two carbon atoms are present between the halogen and oxygen atoms, or a _halo-12 hydrocarbyl oxy gt; All weight percentages are based on the total weight of 2- (2,3-epoxypropyl) phenol, 2-allylphenol and 3-chromanol.

In another embodiment, the present invention provides a process for the preparation of 2-allyl-6-methylphenol, in the presence of a catalyst comprising bis (acetylacetonate) dioxomolybdenum (VI), tungstic acid, tungsten hexacarbonyl, m -chloroperbenzoic acid with an oxidizing agent comprising m -chloroperbenzoic acid.

In another embodiment, the compositions of the present invention comprise, based on the total weight of the composition, from 1% to 90% by weight of 2- (2,3-epoxypropyl) phenol of the structure:

5% to 90% by weight of 2-allylphenol of the formula:

및

And

From 0% to 40% by weight of 3-

Lt; / RTI >

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C ₁ -C ₁₂ hydrocarbyl-oxy, or C ₂ -C for at least two carbon atoms are present between the halogen and oxygen atoms, or a _halo-12 hydrocarbyl oxy gt;

All weight percentages are based on the total weight of 2- (2,3-epoxypropyl) phenol, 2-allylphenol and 3-chromanol.

Another embodiment provides a thermoset polymer prepared by reacting 2-allylphenol of the following formula with an oxidizing agent in the presence of a catalyst,

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C ₁ is -C ₁₂ hydrocarbyl-oxy, or halogen, and that between oxygen atoms at least two carbon atoms are present C ₂ -C ₁₂ halo-hydrocarbyl oxy.

Hereinafter, with reference to the drawings,
1 shows the 400 Mhz ¹ H-NMR spectrum of the reaction mixture of Example 4 containing methanol, unreacted 2-allyl-6-methylphenol, 8-methyl-3-chromanol and hydrogen peroxide, It is.
Figure 2 for 5 hours MoO ₂ (acac) 2- allyl-6-methylphenol in the presence of ₂ during 30 ℃ m- chloroperbenzoic acid and 400 Mhz ¹ H- the reaction mixture of the reaction product that, in Example 3 NMR spectrum and a 2D-correlation (COZY) spectrum.
3 shows a 400 Mhz < ¹ > H-NMR spectrum in the range of 8.2-6.8 ppm of the reaction mixture of Example 3. Fig.
4 shows a 400 Mhz ¹ H-NMR spectrum in the range of 6-2 ppm of the reaction product of Example 3. Fig.
FIG. 5 is a graphical representation of the molecular weight distribution of 2-allyl-6-methyl (meth) acrylate drawn as a function of reaction time in the MoO ₂ (acac) ₂ -catalyzed epoxidation of 2-allyl-6-methylphenol and m- (% By weight) of 2- (2,3-epoxypropyl) -6-methylphenol and the amount (% by weight) of 8-methyl-3-chromanol.
6 is example 16 of 2-allyl-6-methylphenol and m- chloroperbenzoic acid of MoO ₂ Cl ₂ - the drawn phenol, 2-allyl-6-methylpyridine as a function of the reaction time in the catalysed epoxidation (% By weight) of 2- (2,3-epoxypropyl) -6-methylphenol and the amount (% by weight) of 8-methyl-3-chromanol.
FIG. 7 is a graph showing the activity of 2-allyl-6-methylphenol, drawn as a function of reaction time, in the H ₂ WO ₄ -catalyzed epoxidation of 2-allyl-6-methylphenol and m- (% By weight) of 2- (2,3-epoxypropyl) -6-methylphenol and the amount (% by weight) of 8-methyl-3-chromanol.
FIG. 8 is a graph showing the effect of 2-allyl-6-methylphenol, drawn as a function of reaction time, on the W (CO) ₆ -catalyzed epoxidation of 2-allyl-6-methylphenol and m- (% By weight) of 2- (2,3-epoxypropyl) -6-methylphenol and the amount (% by weight) of 8-methyl-3-chromanol.

A process for the production of 2- (2,3-epoxypropyl) phenols which is efficient and inexpensive to make into commercial materials is desirable. The present inventors have identified a direct, one-step route for the preparation of 2- (2,3-epoxypropyl) phenol, the epoxidation of the corresponding 2-allylphenol. 2-Allylphenol is allylphenol in which the allyl group is directly bonded to a phenyl carbon atom and is different from O-allylphenol in which the allyl group is directly bonded to phenol oxygen. The process is applicable to 2-allyl phenols such as 2-allyl-6-methylphenol, and commercially available peroxides such as m-chloroperbenzoic acid can be used. The process has one reaction step-epoxidation of 2-allylphenol. Moreover, the conversion of 2-allylphenol can proceed rapidly, providing a commercially acceptable cycle time.

Thus, a process for preparing 2- (2,3-epoxypropyl) phenol comprises reacting 2-allylphenol with an oxidizing agent in the presence of a catalyst,

The 2-allylphenol

, Wherein the 2- (2,3-epoxypropyl) phenol is selected from the group consisting of

/ RTI >

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C ₁ -C ₁₂ hydrocarbyl-oxy, or C ₂ -C for at least two carbon atoms are present between the halogen and oxygen atoms, or a _halo-12 hydrocarbyl oxy gt; All weight percentages are based on the total weight of 2- (2,3-epoxypropyl) phenol, 2-allylphenol and 3-chromanol. As used herein, the term "hydrocarbyl" broadly includes carbon and hydrogen, and optionally includes 1 to 3 heteroatoms, such as oxygen, nitrogen, halogen, Quot; refers to a monovalent substituent. In some embodiments, the group Z is selected from hydrogen, methyl, and combinations thereof. For example, the process can be used to prepare 2- (2,3-epoxypropyl) -6-methylphenol from 2-allyl-6-methylphenol.

The catalyst may be a transition metal catalyst. For example, the catalyst may be a transition metal catalyst comprising molybdenum, vanadium, tungsten, titanium, manganese, niobium or combinations thereof. The transition metal may be in an IV, V, or VI oxidation state, such as Ti (IV), Nb (V), Mn (VI), Mo (VI) or W (VI). Specific examples of the catalyst include bis (acetylacetonato) dioxomolybdenum (VI) (MoO ₂ (acac) ₂ ), molybdenum dichloride dioxide (MoO ₂ Cl ₂ ), tungstic acid (H ₂ WO ₄ ) (CO) ₆ , molybdenum hexacarbonyl (Mo (CO) ₆ ), vanadium acetylacetonate (V (acac) ₂ ), vanadium (H ₄ O ₄₀ SiW ₁₂ .xH ₂ O), tungsten hexacarbonyl But are not limited to, diacetylacetonate (VO (acac) ₂ ), vanadium pentoxide (V ₂ O ₅ ), or combinations thereof. In some embodiments, the catalyst comprises bis (acetylacetonato) dioxomolybdenum (VI), molybdenum dichloride dioxide, tungstic acid, tungsten hexacarbonyl, or combinations thereof. The catalyst may also be an inhomogeneous catalyst on an inert solid support, for example silica or alumina.

The oxidizing agent may comprise an organic peroxide, i.e. an organic compound containing a peroxy "-OO-" group. In particular, the oxidizing agent may be selected from the group consisting of hydrogen peroxide, alkyl peroxide, alkyl hydroperoxide, ketone peroxide, diacyl peroxide, peroxyketal, peroxy ester, peroxydicarbonate, peroxy acid, And combinations of these. Examples of the oxidizing agent include hydrogen peroxide, 2-butanone peroxide, cyclohexanone peroxide, benzoyl peroxide, lauryl peroxide, di- tert -butyl peroxide, tert -butyl cumyl peroxide, peroxide, tert - butyl hydroperoxide, cumene hydroperoxide, tert - butyl peroxybenzoate, tert - amyl buffer Oaks benzoate, tert - butyl peroxy octoate, 2,2-di (tert - butylperoxy) Butane, 2,2-di ( tert -butylperoxy) octane, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (tert - butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert - butylperoxy) hex-3-Ain, 1, 4-(tert - butyl peroxy isopropyl) benzene, 3-di (tert - butyl peroxy isopropyl) benzene, di (tert - butylperoxy) isophthalate, formate buffer, buffer acetamide , Buffer acid, buffer acid, buffer isovaleric acid, buffer acid, perbenzoic acid, m - chloroperbenzoic acid, mono-acid buffer, p - methoxy Tox perbenzoic acid, m - knit chloroperbenzoic acid, naphthoic acid buffer α-, β- Per (naphthoic acid), di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide, and combinations thereof. In some embodiments, the oxidizing agent comprises m -chloroperbenzoic acid (MCPBA), and in some embodiments, the oxidizing agent comprises hydrogen peroxide.

The process may optionally be carried out in the presence of a solvent. As reported in Example 1, substantial factors can be considered in selecting the solvent, including the cost, health hazards, solubility, oxidant, and solubility of the catalyst, and boiling point of the 2-allylphenol. For example, the solvent may be a non-polar solvent such as benzene, toluene, ethylbenzene, cumene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, chloroform or combinations thereof. The solvent may also be a polar solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, dimethyloxyethane, tetrahydrofuran, 1,4- dioxane, dimethylformamide, dimethylsulfoxide , Acetonitrile, or combinations thereof. Any combination of the above solvents, including combinations of polar and non-polar solvents, may also be used. Methanol or 2-propanol is advantageous due to easy removal from the product by distillation, miscibility with aqueous hydrogen peroxide and low cost. Thus, in some embodiments, the solvent comprises methanol, 2-propanol, or a combination thereof. The solvent may also be water. Toluene and chloroform are advantageous because they are good solvents for 2-allylphenol and 2- (2,3-epoxypropyl) phenol and are poor solvents for catalysts, thus simplifying catalyst removal and product isolation. Thus, in some embodiments, the solvent comprises toluene, chloroform, or a combination thereof.

Epoxidation can be carried out over a wide range of temperature and time ranges, depending in part on the particular oxidizing agent and catalyst used. As used herein, the terms "epoxidation" and "reaction" both refer to the process of the present invention for preparing 2- (2,3-epoxypropyl) phenol from 2-allylphenol in the presence of an oxidizing agent and a catalyst . The reaction temperature is balanced between the reaction time and the rate of oxidative decomposition. If the temperature is too low, the reaction will take too long. If the reaction temperature is too high, the oxidizing agent will decompose before the oxidant has an opportunity to react with 2-allylphenol. To achieve an economically feasible reaction time, the minimum reaction temperature may be -20 占 폚, 0 占 폚 or 20 占 폚. The maximum temperature is determined in part by the decomposition temperature of the oxidizing agent. For example, m -chloroperbenzoic acid begins to decompose at about 80 ° C. For some oxidizing agents including m -chloroperbenzoic acid, the reaction temperature may be from -20 캜 to 80 캜, specifically from 0 캜 to 60 캜, more specifically from 20 캜 to 40 캜. Hydrogen peroxide begins to decompose at about 40 ° C. Thus, when hydrogen peroxide is used as the oxidizing agent, the reaction temperature may be from -20 占 폚 to 50 占 폚, specifically from 0 占 폚 to 45 占 폚, and more specifically, from 20 占 폚 to 40 占 폚. The reaction time may be 10 minutes to 8 hours, specifically 20 minutes to 6 hours, more specifically 30 minutes to 4 hours. In some embodiments, the reaction temperature is between -10 ° C and 50 ° C, and the reaction time is between 10 minutes and 6 hours.

At any reaction temperature, the conversion% depends on the oxidant, the activity of the catalyst, and the reaction time. For example, if m -chloroperbenzoic acid is used as the oxidizing agent and a molybdenum catalyst such as MoO ₂ (acac) ₂ and MoO ₂ Cl ₂ is used, 50% conversion of 2-allylphenol occurs within the first 10 minutes 5 and 6). When m -chloroperbenzoic acid is used as the oxidizing agent and tungsten catalysts such as H ₂ WO ₄ and W (CO) ₆ are used, 60% conversion of 2-allylphenol occurs within the first 30 minutes and another 20% The conversion occurs over 70 minutes (Figs. 7 and 8). In some embodiments, the 2-allylphenol is converted from 50% to 100% within 10 minutes to 6 hours at the reaction temperature of -10 ° C to 50 ° C.

In some embodiments, the 2-allylphenol comprises 2-allyl-6-methylphenol and the 2- (2,3-epoxypropyl) phenol comprises 2- (2,3-epoxypropyl) . The process for the preparation of 2- (2,3-epoxypropyl) -6-methylphenol is carried out in the presence of a catalyst comprising bis (acetylacetonate) dioxomolybdenum (VI), tungstic acid, tungsten hexacarbonyl, , 2-allyl-6-methylphenol with an oxidizing agent comprising m -chloroperbenzoic acid.

In the epoxidation reaction, 3-chromanol of the following structure can be formed:

In the above formulas, Z is independently as defined for 2-allylphenol and 2- (2,3-epoxypropyl) phenol. Thus, a mixture of 2- (2,3-epoxypropyl) phenol and 3-chromanol can be formed. In some embodiments, the composition comprises 0 wt% to 40 wt%, specifically 1 wt% to 40 wt%, more specifically 1 wt% to 20 wt% 3-chromanol, based on the total weight of the composition By weight. Furthermore, if the conversion of the 2-allyl phenol is incomplete, a mixture of 2-allylphenol, 2- (2,3-epoxypropyl) phenol and 3-chromanol may be formed. Thus, in some embodiments, the reaction of the 2-allylphenol and the oxidizing agent in the presence of a catalyst comprises, based on the total weight of the composition, from 1% to 90% by weight of 2- (2,3-epoxypropyl)

5% to 90% by weight of 2-allylphenol of the formula:

및

And

From 0% to 40% by weight of 3-

, ≪ / RTI >

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C ₁ -C ₁₂ hydrocarbyl-oxy, or C ₂ -C for at least two carbon atoms are present between the halogen and oxygen atoms, or a _halo-12 hydrocarbyl oxy gt; All weight percentages are based on the total weight of 2- (2,3-epoxypropyl) phenol, 2-allylphenol and 3-chromanol.

In some embodiments, the 2- (2,3-epoxypropyl) phenol comprises 2- (2,3-epoxypropyl) -6-methylphenol, the 2-allylphenol comprises 2-allyl- , ≪ / RTI > 3-chromanol

, Which is also referred to herein as "8-methyl-3-chromanol" or "MCO". The composition of the present invention comprises 0% to 40% by weight, specifically 1% to 40% by weight, more specifically 1% by weight to 8% by weight, based on the total weight of the composition, 20% by weight. Thus, in some embodiments, the composition comprises, based on the total weight of the composition, from 1% to 90% by weight of 2- (2,3-epoxypropyl) -6-methylphenol, 5 to 90% by weight and 8 to 30% by weight of 8-methyl-3-chromanol.

Depending on the catalyst, the amount of 2- (2,3-epoxypropyl) phenol produced may decrease with time as a result of the secondary cyclization reaction to form 3-chromanol from 2-allylphenol. For example, FIG. As can be seen in Figure 5, a 2-allyl phenol is 2-allyl-6-methylphenol, and when the oxidizing agent is m- chloroperbenzoic acid, catalyst is _{MoO 2 (acac) 2, 2-} (2 , 3-epoxypropyl) -6-methylphenol in an amount of up to about 35% by weight within the first 20 minutes of the reaction. The final amount of 2- (2,3-epoxypropyl) -6-methylphenol was about 30% by weight. Thus, in some embodiments, the composition comprises, based on the total weight of 2- (2,3-epoxypropyl) -6-methylphenol, 2-allyl-6-methylphenol, and 8- 1 to 40% by weight of 2- (2,3-epoxypropyl) -6-methylphenol, 30 to 90% by weight of 2-allyl-6-methylphenol and 1% To 40% by weight. As can be seen in FIG. 6, when MoO ₂ Cl ₂ was used, 2- (2,3-epoxypropyl) -6-methylphenol was obtained in an amount of up to 15% by weight within 10 minutes. After about 22 minutes, 2- (2,3-epoxypropyl) -6-methylphenol was observed, but 25 wt% 8-methyl-3-chromanol was formed. As can be seen in FIG. 7, 65% by weight 2- (2,3-epoxypropyl) -6-methylphenol was obtained within the first 20 minutes when using H ₂ WO ₄ and 85% 2- 3-epoxypropyl) -6-methylphenol were obtained after an additional 80 minutes. As can be seen in FIG. 8, the results using W (CO) ₆ were similar to those using H ₂ WO ₄ . Thus, in some embodiments, the composition comprises, based on the total weight of the composition, 2- (2,3-epoxypropyl) -6-methylphenol, 2-allyl- 5 to 90% by weight of 2- (2,3-epoxypropyl) -6-methylphenol, 5 to 90% by weight of 2-allyl-6-methylphenol and 8 to 90% Methyl-3-chromanol in an amount of 1 wt% to 20 wt%.

Under some conditions, a thermosetting polymer can be formed by the reaction of an oxidizing agent with a 2-allylphenol, such as 2-allyl-6-methylphenol, in the presence of a catalyst. The glass transition temperature of the thermosetting polymer may be from 230 캜 to 260 캜, specifically from 230 캜 to 250 캜, more specifically from 235 캜 to 245 캜. In particular, the reaction of 2-allyl-6-methylphenol and an oxidizing agent in the presence of a catalyst can produce a thermosetting polymer having a glass transition temperature of 235 ° C to 245 ° C. For example, the reaction of 2-allyl-6-methylphenol with aqueous hydrogen peroxide in the presence of MoO ₂ (acac) ₂ and methanol as in Example 4, Heating at 65 占 폚 produced a thermosetting polymer having a glass transition temperature of 241 占 폚.

The present invention includes at least the following embodiments.

Embodiment 1: A process for producing 2- (2,3-epoxypropyl) phenol, comprising reacting 2-allylphenol with an oxidizing agent in the presence of a catalyst,

The 2-allylphenol

, Wherein the 2- (2,3-epoxypropyl) phenol is selected from the group consisting of

/ RTI >

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halohydrocarbyloxy wherein at least two carbon atoms are present between the halogen and the oxygen atom,

A process for producing 2- (2,3-epoxypropyl) phenol.

Implementation 2:

In embodiment 1,

Wherein the 2-allyl phenol comprises 2-allyl-6-methylphenol,

A process for producing 2- (2,3-epoxypropyl) phenol, characterized in that the 2- (2,3-epoxypropyl) phenol comprises 2- (2,3-epoxypropyl) .

Implementation 3:

In Embodiment 1 or 2,

Wherein the catalyst is a transition metal catalyst comprising molybdenum, vanadium, tungsten, titanium, manganese, niobium or a combination thereof.

Implementation Example 4:

In any of embodiments 1 to 3,

Characterized in that the catalyst comprises bis (acetylacetonato) dioxomolybdenum (VI), molybdenum dichloride dioxide, tungstic acid, tungsten hexacarbonyl or a combination thereof. ≪ / RTI >

Implementation Example 5:

In any of embodiments 1-4,

Wherein the oxidant is selected from the group consisting of hydrogen peroxide, alkyl peroxide, alkyl hydroperoxide, ketone peroxide, diacyl peroxide, peroxyketal, peroxy ester, peroxydicarbonate, peroxy acid, (2, 3-epoxypropyl) phenol. ≪ / RTI >

Implementation Example 6:

In any of embodiments 1-5,

Wherein the oxidant comprises m-chloroperbenzoic acid. ≪ RTI ID = 0.0 > 21. < / RTI >

Implementation Example 7:

In any of embodiments 1 to 6,

Wherein the oxidizing agent comprises hydrogen peroxide. ≪ RTI ID = 0.0 > 21. < / RTI >

Embodiment 8:

In any of embodiments 1 to 7,

The reaction temperature is from -10 DEG C to 50 DEG C,

Wherein the reaction time is from 10 minutes to 6 hours. ≪ RTI ID = 0.0 > 2- (2,3-epoxypropyl) phenol < / RTI >

Embodiment 9:

In any of embodiments 1 to 8,

Characterized in that 50% to 100% of the 2-allylphenol is converted at a reaction temperature of -10 ° C to 50 ° C within 10 minutes to 6 hours.

Embodiment 10:

In any of embodiments 1 to 9,

A process for preparing 2- (2,3-epoxypropyl) phenol characterized in that there is a selectivity of 50% to 100% for 2- (2,3-epoxypropyl) phenol.

Implementation Example 11:

In any of embodiments 1 to 10,

3-chroma < / RTI >

Is prepared with the above 2- (2,3-epoxypropyl) phenol,

(2, 3-epoxypropyl) phenol, wherein Z is as defined in Embodiment 1.

Embodiment 12:

In any of embodiments 1 to 11,

Wherein the 2-allyl phenol comprises 2-allyl-6-methylphenol;

Wherein the 2- (2,3-epoxypropyl) phenol comprises 2- (2,3-epoxypropyl) -6-methylphenol;

Wherein the oxidant comprises m -chloroperbenzoic acid;

Characterized in that the catalyst comprises bis (acetylacetonate) dioxomolybdenum (VI), tungstic acid, tungsten hexacarbonyl or a combination thereof.

Embodiment 12a:

In the presence of a catalyst comprising bis (acetylacetonate) dioxomolybdenum (VI), tungstic acid, tungsten hexacarbonyl, or a combination thereof, with 2-allyl-6-methylphenol in the presence of an oxidizing agent comprising m -chloroperbenzoic acid (2, 3-epoxypropyl) -6-methylphenol. ≪ / RTI >

Implementation Example 13:

As a composition,

The composition

2- (2,3-epoxypropyl) phenol of the following structure: 1 wt% to 90 wt%

5% to 90% by weight of 2-allylphenol of the formula:

및

And

From 0% to 40% by weight of 3-

Lt; / RTI >

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C ₁ -C ₁₂ hydrocarbyl-oxy, or C ₂ -C for at least two carbon atoms are present between the halogen and oxygen atoms, or a _halo-12 hydrocarbyl oxy gt;

All weight percentages are based on the total weight of 2- (2,3-epoxypropyl) phenol, 2-allylphenol and 3-chromanol.

Embodiment 14:

In embodiment 13,

Wherein the 2- (2,3-epoxypropyl) phenol comprises 2- (2,3-epoxypropyl) -6-methylphenol,

Wherein the 2-allyl phenol comprises 2-allyl-6-methylphenol,

Wherein the 3-chromanol comprises 8-methyl-3-chromanol.

Implementation Example 15:

In Embodiment 13 or 14,

Based on the total weight of 2- (2,3-epoxypropyl) -6-methylphenol, 2-allyl-6-methylphenol and 8- Methylphenol, 1 wt% to 40 wt% of 2-allyl-6-methylphenol, 1 wt% to 90 wt% of 2-allyl-6-methylphenol and 1 wt% to 40 wt% of 8- Lt; / RTI >

Implementation Example 16:

In embodiment 13,

Based on the total weight of 2- (2,3-epoxypropyl) -6-methylphenol, 2-allyl-6-methylphenol and 8- Methylphenol in an amount of 5 to 90% by weight, 5 to 90% by weight of 2-allyl-6-methylphenol and 1 to 20% by weight of 8-methyl- Lt; / RTI >

Implementation Example 17:

A thermosetting polymer produced by reacting 2-allylphenol of the following structural formula with an oxidizing agent in the presence of a catalyst,

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halohydrocarbyloxy wherein at least two carbon atoms are present between the halogen and the oxygen atom.

Embodiment 18:

In embodiment 17,

Wherein the 2-allyl phenol comprises 2-allyl-6-methylphenol,

Wherein the thermosetting polymer has a glass transition temperature of 235 캜 to 245 캜.

The invention is further illustrated by the following non-limiting examples.

Example

The materials used in the examples are listed in Table 1 below.

matter CAS number Chemical name water
(weight%) Abbreviation 3354-58-3 2-allyl-6-methylphenol 50% AMP 1567906-11-9 2- (2,3-epoxypropyl) -6-methylphenol Variable EMP 136514-01-7 8-methyl-3-chromanol Variable MCO 7722-84-1 Aqueous H ₂ O ₂ / H ₂ O 50% - 75-05-8 Acetonitrile > 99.9% - 67-66-3 chloroform > 99.9% - 865-49-6 Chloroform-d 99.8% CDCl ₃ 68-12-2 N, N-dimethylformamide > 99.9% DMF 123-91-1 1,4-dioxane > 99% - 67-56-1 Methanol 99% - 78-93-3 Methyl ethyl ketone > 99% MEK 109-99-9 Tetrahydrofuran > 99.9% THF 108-88-3 toluene 99% - 937-14-4 m-Chloroperbenzoic acid 77% MCPBA 63393-96-4 Trioctyl monomethylammonium chloride 99% ALIQUAT ™ 336 139-13-9 2,2 ', 2 "-nitrilotriacetic acid - NTA 13939-06-5 Molybdenum hexacarbonyl 99.9% - 17524-05-9 Bis (acetylacetonato) dioxomolybdenum (VI) - MoO ₂ (acac) ₂ 13637-68-8 Molybdenum dichloride dioxide - MoO ₂ Cl ₂ 14040-11-0 Tungstic acid hydrate 97% H ₂ WO ₄ 7783-03-1 Tungsten hexacarbonyl 99% W (CO) ₆ 12027-43-9 Tungstosylic acid 99.9% H ₄ O ₄₀ SiW ₁₂ .xH ₂ O 13476-99-8 Vanadium acetylacetonate 97% V (acac) ₂ 3153-26-2 Vanadyl acetylacetonate 98% VO (acac) ₂ 1314-62-1 Vanadium pentoxide - V ₂ O ₅

The reaction mixture was characterized by ¹ H-NMR spectroscopy. The ¹ H-NMR spectrum of the reaction mixture is shown in FIGS. 1 to 4. In Figures 2 to 4, the ¹ H-NMR peak is identified by the number corresponding to the hydrogen atom specific to the chemical structure as indicated.

Example 1. Solvent screening

Observations regarding the solubility of 50 wt% H ₂ O 2 / H ₂ O and AMP in various solvents are summarized in Table 2. All solubility studies were performed at room temperature and atmospheric pressure. The oxidizer (aqueous H ₂ O ₂ ) and solute (AMP) were mixed with the solvents listed in Table 2 and the observations were recorded. H ₂ O ₂ and AMP were found to be fully miscible in polar solvents. AMP is soluble in aromatic solvents, whereas aqueous H ₂ O ₂ is insoluble, thus forming two phases. To compare the solvents, ease of solvent separation based on cost, health hazard, H ₂ O ₂ and AMP solubility, catalyst solubility, and boiling point was designated as positive (+) or negative (-) weight . The results are summarized in Table 3. These experiments confirmed methanol as a potential solvent. Methanol is relatively inexpensive and non-hazardous compared to other solvents evaluated. Furthermore, the low boiling point of methanol makes it less energy to separate and recover than other solvents. All of the catalyst candidates except tungstic acid have been found to be insoluble in methanol and can therefore be recovered by filtration. Tungstic acid was slightly soluble in methanol.

Solubility of 50% H ₂ O ₂ / H ₂ O and 2-allyl-6-methylphenol in various solvents system Noteworthy Methanol - Homogeneous single phase was observed. toluene
Test 1:
- Toluene and H ₂ O ₂ were incompatible - two phases were observed.
Two phases were observed despite the introduction of a phase transfer catalyst (20 wt.% NTA in H ₂ O).
Test 2:
The catalyst was evaluated by adding ALIQUAT ™ 336, a phase transfer catalyst, to the mixture of toluene + H ₂ O ₂ . Two phases were observed.
- When AMP was added to the mixture, the color of the solution turned green over time (an indicator of possible reaction). Acetonitrile - Homogeneous single phase was observed. 2-propanol - Homogeneous single phase was observed. MEK ^a - MEK and H ₂ O ₂ formed a milky suspension. Solid agglomerates were observed after a few minutes. This was due to the solubility of poly (acrylonitrile-butadiene-styrene) from the pipette used to transfer the solvent in MEK.
- The test was repeated using a glass pipette. A milky suspension was observed again, indicating that MEK and H ₂ O ₂ Lt; RTI ID = 0.0 > a < / RTI >
- AMP was not added to the mixture. Acetone - Homogeneous single phase was observed. DMF - Homogeneous single phase was observed. ethanol - Homogeneous single phase was observed. THF - Homogeneous single phase was observed. 1,4-dioxane - Homogeneous single phase was observed. chloroform - CHCl ₃ and H ₂ O ₂ were incompatible. Two phases were observed. The phase transfer catalyst can enhance the contact between the two phases. a. Molybdenum poly (acrylonitrile-butadiene-styrene) from a pipette.

Criteria applied for solvent selection menstruum Cost ^b
US $ / liter Hazard (HMIS) ^c H ₂ O ₂ / AMP
Solubility catalyst
Solubility ^d Solvent separation
(bp ° C) Methanol + (45) + (1) + + + (64.7) toluene + (63) - (3) - + - (110) Acetonitrile - (143) - (3) + + - (81) 2-propanol + (61) - (2) + + - (82) MEK ^a - (77) - (2) - + - (80) Acetone - (75) - (2) + + + (56) DMF - (109) - (2) + + - (102) ethanol - (95) - (2) + + - (78) THF - (85) - (2) + + + (65) 1,4-dioxane - (147) - (2) + + - (100) chloroform - (88) - (2) - + + (60.5) a. Molybdenum poly (acrylonitrile-butadiene-styrene) from a pipette.
b. Cost estimates are based on qualitative, small-volume CHROMASOLV ™ grade solvent procurement. Pricing information was obtained from Sigma-Aldrich. A price higher than US $ 70 per liter was considered undesirable.
c. Two or more HMIS health hazards were considered undesirable.
d. "+" Indicates that the catalyst was insoluble. Insolubility of the catalyst forming the heterogeneous reaction mixture solves the problem of catalyst separation.

Example 2. Aqueous H ₂ O ₂ and MoO ₂ (acac) ₂ -catalyzed epoxidation of 2-allyl-6-methylphenol

The reaction mixture (AMP + H ₂ O _{2 + CH 3 OH + MoO 2 (} acac) 2) was colorless at first, and changes to dark brown within the first 30 minutes of the reaction. This color change may be due to the formation of molybdenum dioxide species (resulting in a change in molybdenum oxidation state). The results obtained were greatly different depending on the reaction temperature. When the reaction temperature was as low as 15-20 ° C, the signal intensity of AMP (measured by GC / MS, peak height of AMP by GC) was found to be similar in both the initial sample and the final sample, The absence of a reaction. On the other hand, a significant decrease in the peak area for AMP peaks (as confirmed by GC / MS and ¹ H-NMR) was observed at higher temperatures of 40 ° C.

The theoretical mass of the product ion estimated and the mass obtained by GC / MS analysis of the reaction mixture were consistent with the formation of EMP. The non-availability of EMP external standards, and the absence of model MS spectra for EMP in the instrument database and open literature, has reduced the reliability of chemical structures predicted by MS software. Furthermore, the same exact mass for the epoxidized AMP (EMP) and the cyclized AMP (8-methyl-3-chromanol) eliminated the use of MS to distinguish these reaction products.

Figure 1 shows the ¹ H-NMR spectrum of the reaction mixture of Example 4 containing unreacted AMP, methanol, 8-methyl-3-chromanol. As can be seen from Fig. 1, the decrease in the intensity of the absorption peak at 7 ppm (doublet state) and 6.7 ppm (triplet state) compared to the same peak in the ¹ H-NMR spectrum of unreacted AMP, Quot; 1 "in the AMP, suggesting that the reaction of the carbon-carbon double bond of AMP has occurred. A busy ¹ H-NMR spectrum coupled with an overbearing absorption peak from methanol interfered with the confirmation of EMP by ¹ H-NMR. The sample needed to be cleaned prior to analysis, via removal of methanol and residual hydrogen peroxide.

Similar results, reduction in the intensity of the absorption peaks corresponding to carbon-carbon double bonds and formation of additional peaks were also obtained when both W-based catalysts and other Mo-based catalysts were used in the epoxidation reaction. Thus, the reaction of carbon-carbon double bonds of AMP has been demonstrated.

Examples 3 to 14. 14. Metal-catalyzed epoxidation of 2-allyl-6-methylphenol

The problems associated with the identification of the reaction product of Example 2 were resolved by carrying out the AMP epoxidation reaction in CDCl ₃ instead of methanol. The use of CDCl ₃ eliminated the need for solvent separation, so that the product could be conclusively identified by NMR, without the need to heat or otherwise concentrate the sample. Due to the immiscibility of H ₂ O ₂ with chloroform, MCPBA was used as an alternative to H ₂ O ₂ . By performing a catalyst screening study in CDCl ₃ instead of methanol or chloroform, the time required for sample preparation was also shortened.

The metal-catalyzed epoxidation of AMP with MCPBA or H ₂ O ₂ was studied to identify the best catalyst for the selective formation of EMP. The reactants and results of Examples 3 to 13 are summarized in Table 4. Most of the catalyst studies were carried out using the following reagents: AMP + MCPBA + catalyst. In Example 4, Example 9 and Example 11, MCPBA was replaced with H ₂ O ₂ . The solvents were CDCl ₃ in Example 1, Examples 3 to 10, and Examples 12 to 14. In Examples 4 and 11, CDCl ₃ was replaced with methanol.

The initial composition of the reaction mixture was ^{5.02x10 - 3 mol AMP + 8.6x10 -} 3 mol oxidant was + 0.18 mol solvent. The oxidant was CDCl ₃ and methanol or MCPBA in CDCl ₃ 50 _{wt% H 2 O 2 / H 2} O during use. The reaction was carried out at 25 [deg.] C for 6 hours. % Conversion (column 3) of AMP in the reaction of AMP with MCPBA or 50 wt% H ₂ O ₂ / H ₂ O and various metal catalysts, and the amount and selectivity for EMP (column 4) and 8- The amount and selectivity for Chromanols (column 5) are summarized in Table 4. The exotherm was observed in Example 4, Example 9, and Example 11 where the oxidizing agent was 50 wt% H ₂ O ₂ / H ₂ O. When a vanadium catalyst was used in combination with 50 wt% H ₂ O ₂ / H ₂ O, highly exothermic decomposition of H ₂ O ₂ was observed when the catalyst was introduced into the reaction mixture. Pyrogenic H ₂ O ₂ decomposition was observed even at very low vanadium catalyst loading. MCPBA was soluble in CDCl ₃ , whereas m-chloroperbenzoic acid formed after transferring the oxygen atom to AMP, which is a by-product of the reaction, was insoluble. Thus, the formation of insoluble solids in epoxidation with MCPBA serves as an indirect indicator of this reaction. The absence of MCPBA decomposition in the presence of the catalyst was confirmed in a separate test.

The ¹ H-NMR spectrum of the product mixture obtained after epoxidation of AMP and MCPBA in the presence of a CDCl ₃ metal catalyst was relatively clear compared to the NMR spectrum of the reaction product obtained in methanol. In Example 5 and Example 8, the formation of EMP was confirmed by ¹ H-NMR spectroscopy. The reaction mixture was also studied by 2D-Correlation Spectroscopy (COZY). An exemplary COZY spectrum of the reaction mixture is reproduced in Fig. The presence of 8-methyl-3-chromanol was confirmed from the COZY spectrum. The formation of 8-methyl-3-chromanol is an intramolecular cyclization reaction and may be due to the reaction between the phenolic hydroxyl group and the epoxide group of the EMP. The ¹ H-NMR spectrum of the reaction product confirmed that the absorption peak corresponds to 8-methyl-3-chromanol by COZY spectroscopy. Once the 8-methyl-3-chromanol peak was identified, standard ¹ H-NMR spectroscopy was used to quantify the amount of 8-methyl-3-chromanol in the reaction product in the catalyst screening study summarized in Table 4 Respectively. The carbon-carbon double bond present in the allyl side chain of AMP underwent epoxidation and EMP was formed. 8-methyl-3-chromanol could be formed by intramolecular cyclization of EMP. Thus, the formation of 8-methyl-3-chromanol suggests at least the formation of EMP as an intermediate product. Almost complete selectivity for 8-methyl-3-chromanol as identified by ¹ H-NMR spectroscopy suggests that a long reaction time is helpful in the cyclization of the EMP. Besides the long reaction time, the easy formation of 8-methyl-3-chromanol may also be due to the high reactivity of the epoxide groups and the absence of steric hindrance to the formation of the chroman ring.

Example 3. MCPBA and MoO ₂ (acac) ₂ catalyst

To 0.75 mL of AMP, 1.5 g of MCPBA, 400 mg of MoO ₂ (acac) _2, and CDCl ₃ were filled in a container. The vessel was placed in an ice bath and allowed to cool. The mixture was stirred using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 4. Aqueous H ₂ O ₂ And MoO ₂ (acac) ₂ catalyst

3 mL of AMP, 4 mL of 50 wt% H ₂ O ₂ / H ₂ O, 400 mg of MoO ₂ (acac) ₂ , and methanol were charged to the vessel. The reaction was carried out under near ambient conditions and the mixture was stirred using a magnetic stir bar. After stirring at 25 [deg.] C for 6 hours, the reaction mixture was analyzed by GC-MS.

Example 5. MCPBA and MoO ₂ Cl ₂ catalyst

0.75 mL of AMP, 1.5 g of MCPBA, 400 mg of MoO ₂ Cl ₂ , and CDCl ₃ were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 6. MCPBA and Mo (CO) ₆ catalyst

0.75 mL of AMP, 1.5 g of MCPBA, 400 mg of Mo (CO) ₆ , and CDCl ₃ were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 7. mcpba and H ₂ WO ₄ catalyst

0.75 mL of AMP, 1.5 g of MCPBA, 200 mg of H ₂ WO ₄ , and CDCl ₃ were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 8. Synthesis of MCPBA and W (CO) ₆ catalyst

0.75 mL of AMP, 1.5 g of MCPBA, 200 mg of W (CO) ₆ , and CDCl ₃ were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 9. Aqueous H ₂ O ₂ and W (CO) ₆ catalyst

0.75 mL of AMP, 4 mL of 50 wt% H ₂ O ₂ / H ₂ O, 200 mg of W (CO) ₆ , and CDCl ₃ were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 10 mcpba and H ₄ O ₄₀ SiW ₁₂ xH ₂ O catalysts

0.75 mL of AMP, 1.5 g of MCPBA, 200 mg of H ₄ O ₄₀ SiW ₁₂ .xH ₂ O, and CDCl ₃ were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 11. Aqueous H ₂ O ₂ and H ₄ O ₄₀ SiW ₁₂ .xH ₂ O catalysts

0.75 mL of AMP, 4 mL of 50 wt% H ₂ O ₂ / H ₂ O, 200 mg of H ₄ O ₄₀ SiW ₁₂ .xH ₂ O, and methanol were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 12. MCPBA and V (acac) ₂ catalyst

0.75 mL of AMP, 1.5 g of MCPBA, 250 mg of V (acac) ₂ , and CDCl ₃ were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 13. MCPBA and VO (acac) ₂ catalyst

0.75 mL of AMP, 4 mL of 50 wt% H ₂ O ₂ / H ₂ O, 250 mg of VO (acac) ₂ , and CDCl ₃ were charged to the vessel. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

Example 14. MCPBA and V ₂ O ₅ catalysts

To 0.75 mL of AMP, 1.5 g of MCPBA and 250 mg of V ₂ O ₅ it was filled in a container. The vessel was cooled in an ice bath while stirring the mixture using a magnetic stir bar. After stirring at 25 ° C for 6 hours, the reaction mixture was analyzed by ¹ H-NMR.

In the metal-catalyzed epoxidation of AMP,% conversion of AMP, yield to EMP and MCO Example catalyst Oxidant AMP
(conversion%) EMP ^b
(mole%) MCO ^b
(mole%) 3 MoO ₂ (acac) ₂ MCPBA 21 - 21 (100) 4 MoO ₂ (acac) ₂ 50 wt% H ₂ O ₂ / H ₂ O in CH ₃ OH 27 - 27 (100) 5 MoO ₂ Cl ₂ MCPBA 59.9 29 (48) 29.9 (50) 6 Mo (CO) ₆ MCPBA 0 - - 7 H ₂ WO ₄ MCPBA 92.5 - 92.5 (100) 8 W (CO) ₆ MCPBA 98.1 20.6 (21) 77.5 (79) 9 W (CO) ₆ CDCl ₃ 50 wt% H ₂ O ₂ / H ₂ O 1.6 - 1.6 (100) 10 H ₄ O ₄₀ SiW ₁₂ .xH ₂ O MCPBA 0 - - 11 H ₄ O ₄₀ SiW ₁₂ .xH ₂ O 50 wt% H ₂ O ₂ / H ₂ O in CH ₃ OH 13.7 - 13.7 (100) 12 V (acac) ₂ MCPBA 0 - - 13 ^a VO (acac) ₂ MCPBA 9+ - 9 a) In addition to MCO, a number of by-products were formed, which were not fully characterized.
b)% selectivity for EMP or MCO based on reacted AMP is given in parentheses.

When MoO ₂ (acac) ₂ was used as the epoxidation catalyst (Example 3 and Example 4), no EMP was detected, indicating that any EMP formed was cyclized to 8-methyl-3-chromanol do. The conversion of AMP to W (CO) ₆ -catalyzed reaction was much higher when MCPBA (Example 8) was used than with H ₂ O ₂ (Example 9). EMP was observed when MCPBA was used as the oxidant in the W (CO) ₆ -catalyzed reaction (Example 8) and the MoO ₂ Cl ₂ -catalyzed reaction (Example 5). Reaction failure of AMP in Example 9 may be due to limited mass transfer between the two phases of the biphasic H ₂ O ₂ / H ₂ O + CDCl ₃ reaction mixture. H ₂ O ₂ was present in the aqueous phase and AMP was present in the organic phase (CDCl ₃ ). Among all the catalysts tested, four catalysts, MoO ₂ (acac) ₂ , MoO ₂ Cl ₂ , W (CO) ₆ and H ₂ WO ₄ were selected for good catalytic activity. A catalyst study was conducted while sampling at regular time intervals to optimize the reaction time, which is a parameter that determines the EMP yield.

Examples 15 to 18. Kinetic studies of metal-catalyzed epoxidation of 2-allyl-6-methylphenol

The amounts of AMP, EMP and 8-methyl-3-chromanol are shown in Figures 5 to 8, respectively, as a function of the reaction time for the metal-catalyzed epoxidation of AMP in Examples 15-18. In the figures,% conversion of AMP is represented by filled diamond; The amount of EMT is indicated by a filled rectangle; The amount of 8-methyl-3-chromanol is indicated by a filled triangle. In each example, the oxidant was MCPBA and the solvent was CDCl ₃ .

In Example 15 and Fig. 5, the conversion rate of AMP in the presence of MoO ₂ Cl ₂ was about 60%. Approximately 90% of this AMP amount was consumed within the first 20 minutes. The amount of EMP and the amount of 8-methyl-3-chromanol were both about 30%. By comparison, in Example 16 and FIG. 6, the AMP conversion rate in the presence of MoO ₂ (acac) ₂ was only about 25%, and no EMP was observed even after the first 20 minutes. A higher selectivity for EMP was observed when using W-based catalysts as compared to Mo-based catalysts. In Example 17 and Fig. 7, the AMP conversion rate in the presence of tungstic acid was about 90%. The amounts of EMP and 8-methyl-3-chromanol were about 80% and about 10%, respectively. In Example 18 and Fig. 8, when W (CO) ₆ was used, the AMP conversion rate was about 80%. About 80% of this AMP amount was converted within the first 30 minutes. The amounts of EMP and 8-methyl-3-chromanol were about 70% and about 10%, respectively. As can be seen in Figures 15-18, 8-methyl-3-chromanol was formed early in the reaction. Thus, optimization (minimization) of the reaction time will not eliminate the formation of 8-methyl-3-chromanol.

Example 19. Thermosetting polymer derived from 2-allyl-6-methylphenol

After first evaporating methanol from the reaction product of Example 4 at about 60-70 ° C under a nitrogen blanket, efforts to directly identify the formation of EMP by ¹ H-NMR spectroscopy failed. Upon removal of the solvent, a powder was formed which was insoluble in both chloroform and DMSO, suggesting the formation of a crosslinked polymer. Thermal analysis using DSC confirmed that the insoluble powder was a thermosetting polymer having a glass transition temperature (T _g ) of 241 ° C. Additional thermal characterization of this material using TGA was carried out at 600 ° C, 700 ° C and 800 ° C in air with 16.47%, 16.60% and 16.58% of char mass, respectively, and when analyzed under a nitrogen atmosphere, 75.64% (600 ° C), 70.81% (700 ° C) and 62.90% (800 ° C).

As used herein, the terms "hydrocarbyl" and "hydrocarbon" broadly include carbon and hydrogen and optionally one heteroatom such as oxygen, nitrogen, halogen, To three substituents. The use of the terms "a", "an", "the" and similar reference expressions in the context of describing the invention (especially in the context of the following claims) Quot; and " plural " unless the context clearly dictates otherwise. Quot; or "means" and / or ". The endpoints of all ranges for the same component or characteristic are inclusive and can be combined independently. In addition to the broader or larger group, the disclosure of a narrower or more specific group does not deny a broader range or a larger group. All ranges disclosed herein include an end point, wherein the end points are independently combinable. As used herein, the terms "first" and "second" and the like do not refer to any order, amount, or importance, and are used to distinguish one element from another. As used herein, "comprising" includes " consisting essentially of "or" consisting "of the listed elements.

Unless defined otherwise, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. "Combination" includes blends, mixtures, reaction products, and the like.

While the exemplary embodiments have been shown for purposes of illustration, the above description should not be construed as limiting the scope of the invention. Accordingly, various modifications, adaptations, and alternatives may be resorted to by those skilled in the art without departing from the spirit and scope of the invention.

Claims (18)

A process for preparing 2- (2,3-epoxypropyl) phenol, comprising reacting 2-allylphenol with an oxidizing agent in the presence of a catalyst,
The 2-allylphenol

, Wherein the 2- (2,3-epoxypropyl) phenol is selected from the group consisting of

/ RTI >
Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halohydrocarbyloxy wherein at least two carbon atoms are present between the halogen and the oxygen atom,
A process for producing 2- (2,3-epoxypropyl) phenol. The method according to claim 1,
Wherein the 2-allyl phenol comprises 2-allyl-6-methylphenol,
A process for producing 2- (2,3-epoxypropyl) phenol, characterized in that the 2- (2,3-epoxypropyl) phenol comprises 2- (2,3-epoxypropyl) . The method according to claim 1,
Wherein the catalyst is a transition metal catalyst comprising molybdenum, vanadium, tungsten, titanium, manganese, niobium or a combination thereof. 4. The method according to any one of claims 1 to 3,
Characterized in that the catalyst comprises bis (acetylacetonato) dioxomolybdenum (VI), molybdenum dichloride dioxide, tungstic acid, tungsten hexacarbonyl or a combination thereof. ≪ / RTI > 4. The method according to any one of claims 1 to 3,
Wherein the oxidant is selected from the group consisting of hydrogen peroxide, alkyl peroxide, alkyl hydroperoxide, ketone peroxide, diacyl peroxide, peroxyketal, peroxy ester, peroxydicarbonate, peroxy acid, (2, 3-epoxypropyl) phenol. ≪ / RTI > 4. The method according to any one of claims 1 to 3,
Wherein the oxidant comprises m-chloroperbenzoic acid. ≪ RTI ID = 0.0 > 21. < / RTI > 4. The method according to any one of claims 1 to 3,
Wherein the oxidizing agent comprises hydrogen peroxide. ≪ RTI ID = 0.0 > 21. < / RTI > 4. The method according to any one of claims 1 to 3,
The reaction temperature is from -10 DEG C to 50 DEG C,
Wherein the reaction time is from 10 minutes to 6 hours. ≪ RTI ID = 0.0 > 2- (2,3-epoxypropyl) phenol < / RTI > 4. The method according to any one of claims 1 to 3,
Characterized in that 50% to 100% of the 2-allylphenol is converted at a reaction temperature of -10 ° C to 50 ° C within 10 minutes to 6 hours. 4. The method according to any one of claims 1 to 3,
A process for preparing 2- (2,3-epoxypropyl) phenol characterized in that there is a selectivity of 50% to 100% for 2- (2,3-epoxypropyl) phenol. The method according to claim 1,
3-chroma < / RTI >

Is prepared with the above 2- (2,3-epoxypropyl) phenol,
(2, 3-epoxypropyl) phenol, wherein Z is as defined in claim 1. 4. The method according to any one of claims 1 to 3,
Wherein the 2-allyl phenol comprises 2-allyl-6-methylphenol;
Wherein the 2- (2,3-epoxypropyl) phenol comprises 2- (2,3-epoxypropyl) -6-methylphenol;
Wherein the oxidant comprises m -chloroperbenzoic acid;
Characterized in that the catalyst comprises bis (acetylacetonate) dioxomolybdenum (VI), tungstic acid, tungsten hexacarbonyl or a combination thereof. As a composition,
The composition
2- (2,3-epoxypropyl) phenol of the following structure: 1 wt% to 90 wt%

5% to 90% by weight of 2-allylphenol of the formula:

And
From 0% to 40% by weight of 3-

Lt; / RTI >
Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C ₁ -C ₁₂ hydrocarbyl-oxy, or C ₂ -C for at least two carbon atoms are present between the halogen and oxygen atoms, or a _halo-12 hydrocarbyl oxy gt;
All weight percentages are based on the total weight of 2- (2,3-epoxypropyl) phenol, 2-allylphenol and 3-chromanol. 14. The method of claim 13,
Wherein the 2- (2,3-epoxypropyl) phenol comprises 2- (2,3-epoxypropyl) -6-methylphenol,
Wherein the 2-allyl phenol comprises 2-allyl-6-methylphenol,
Wherein the 3-chromanol comprises 8-methyl-3-chromanol. 14. The method of claim 13,
Based on the total weight of 2- (2,3-epoxypropyl) -6-methylphenol, 2-allyl-6-methylphenol and 8- Methylphenol, 1 wt% to 40 wt% of 2-allyl-6-methylphenol, 1 wt% to 90 wt% of 2-allyl-6-methylphenol and 1 wt% to 40 wt% of 8- Lt; / RTI > 14. The method of claim 13,
Based on the total weight of 2- (2,3-epoxypropyl) -6-methylphenol, 2-allyl-6-methylphenol and 8- Methylphenol in an amount of 5 to 90% by weight, 5 to 90% by weight of 2-allyl-6-methylphenol and 1 to 20% by weight of 8-methyl- Lt; / RTI > A thermosetting polymer produced by reacting 2-allylphenol of the following structural formula with an oxidizing agent in the presence of a catalyst,

Wherein Z is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbylthio, wherein the hydrocarbyl group is not a tertiary hydrocarbyl group, C C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halohydrocarbyloxy wherein at least two carbon atoms are present between the halogen and the oxygen atom. 18. The method of claim 17,
Wherein the 2-allyl phenol comprises 2-allyl-6-methylphenol,
Wherein the thermosetting polymer has a glass transition temperature of 235 캜 to 245 캜.

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